Compositions comprising an acrylonitrile polymer, an alkali metal or alkaline earth metal thiocyanate, and an aliphatic alcohol



Patented July 20, 1954 COMPOSITIONS COMPRISING AN ACRYLO- NITRILE POLYMER, AN ALKALI METAL OR; ALKALINE EARTH METAL THIDCYANATE, AND' AN ALIPHATIC ALCOHOL Melvin: At Dietrich, Claymont, and Albert F. Smith, Wilmington, DeL', assignors to- E. I. du Pont de Nemours & Company; Wilmington, DeL, a corporation of Delaware No-=Drawing. Application February 7, 1952, Serial No. 270,522

7 14 Claims. 1 This invention relates to thermoplastic acrylonitrile polymer compositions.

Acrylonitrile polymers of predominant'facrylo nitrile content are generally considered nonthermoplastic and are not subject to fabrication of shaped articles by the application of heat and pressure. Organic solvents generally employed for shaping such intractable polymers are disadvantageous, inter alia, in that they are expensive, frequently have toxic properties, and entail difiiculties in recovery. Salt solutionshavebeen suggested as suitable solvents for such relatively inert polymers as polyacrylonitriles, .as shown by U. S. Pat. 2,140,921, but the acrylonitrile content ofthe solution is rather low, 1. e., 6% or less as indicated in the examples. of said patent. Thus, it has not been possible to obtain solutions that have high polymer content or contain large amounts of high molecular weight material since either the viscosityis too highgelation taking place-or theactual solubilityv is too :low. The salt. solutions of polymers heretofore available have been employed to give objects such as films or fibers of relatively thin cross-sectional area by removal of salt and water in a precipitation bath. Such systems, even when improved by the addition of small amounts of an alcohol, as described in McClellan Ser. No. 231,248, filed June 12, 1951, cannot be employed to obtain films, filaments, or moldedobjects through standard thermoplastic fabrication techniques. In addition such. systems require the use of relatively large quantities of solvents.

This invention has as an object a method of preparing films, filaments, and molded objects from polymeric acryloni-trile. Afurther object isthe provision of compositions suitable for said method. Another objectis a'method for the preparation of generally solid (non-fluid) polymeric acrylonitrile compositions useful for fabrication into films or filaments under pressure at elevated temperature. Otherob'jects will appear hereinafter.

These objects are accomplishedby the present invention of solid (non-fluid) compositions containing 33-75% of an acrylonitrile polymer in which acrylonitrile is the major component,-

l8-i6 of alkalior alkaline earth 'thiocyanate, and-33% of an aliphatic alcohol having-at least onealcohol group perfive-carbons,liquid at room temperature and soluble inwater to an extent :of at least 2% at 20 C'., in which compo- The following examplesin which parts are by weightware illustrative of the invention. When films were obtained by use of aCarverpress, the pressure reported is the gauge pressure which correspondsfito a film pressure of the order of 400-1000 lbs/sq. in.

E :vample I A. Ten parts polyacrylonitrile (intrinsic viscosity, 1.95) (33%) an'd'ten parts dry'sodium thiocyanate' (33%) werethoroughly mixed in a mortar. To this mixture, ten parts ethylene glycol(33%) was then added slowly with constant mixing. The mixture initially was powdery. but, on standing, graduallychanged into a plastic gum. This gum could be molded by hand into any shape desired. It could be stretched by hand, resembling rubber somewhat'in this characteristic.

The gum was extruded in a press spinner "at 124 C. through a one hole'(32 mil) spinneret into threeinch'es of water at 15 C. and'wound up manually on abobbin. While still on the bobbin -it was'washed' in running water until free of saltand glycol.v The monofil was drawn, after washing and while still wet, through air or through water to produce filaments with the following properties (after drying).

B. The plastic .gum was pressed at 50 C. and. atf C. between sheets of cellophane on a press at 15,000 lbssto produce'clear films of 9 to 10ml; thickness. After'washing and drying the'filmswere brittle. Calendering dicyclohexylammonium oleate into the gel films, followed by drying, produced tough, clear, and pliable films.

C. The composition described in A was pressed into a film on apressatlOO" C. and 15,000 lbs. pressure. The film was washed, drawn 100% in C. water, while in gel form and then dried. The filmswere tough and pliable. Another film pressed-from this'composition was stretched 3X in the width direction and 3.8K in-the length direction in 90 C. water immediately after pressing. The stretched film was washed in water in taut condition and'dried in the'relaxed condition. It was tough, clear; and pliable.

Example II A series of compositions was prepared in which the ratio of polymer to salt to glycol was varied to give compositions which could be shaped into articles by application of pressure and heat. The compositions were pressed into films in a press at 15,000-17,000 lbs. using temperatures ranging from 140 C. to 220 C. The make-up of these compositions, expressed in terms of parts by weight (and per cent) and the characteristics of the films obtained from them are given in the following table. The polymer used had an intrinsic viscosity of 1.87.

4, ple IV. The composition formed was a soft gum. A film pressed at 150 C. and 17,000 lbs. was clear and bright.

Example VIII An acrylonitrile/diketene copolymer, containing 5% diket'ene, was treated as in Example IV. A bright and clear film was obtained by pressing at 170 C. and 15,000 lbs. The composition from which the film was obtained was a gum.

Example IX When an acrylonitrile/vinyl pyridine copolymer (5% vinyl pyridine) was used as in Example These results Show that workable compositions are obtained in the polymer-salt ratio between about l/1 and /3, and the salt-hydroxy compound ratio lies between 1/1 and 5/1. Compositions falling within these ratios range from stiff gums to powdery solids.

In contrast to this, a composition containing parts (77%) polymer, 5 parts (19%) salt, and one part (4%) glycol gave a brittle film. This composition exceeds the 75% polymer maximum of this invention.

Example III Ten parts of a oopolymer of acrylonitrile and styrene, containing 14.5% styrene and having an intrinsic viscosity of 1.83, were mixed with 10 parts sodium thiocyanate and 10 parts ethylene glycol to form a plastic gum. Films pressed from this composition in a press at 70 C. were tough,

while wet.

clear, and pliable Example IV Ten parts of a copolymer of acrylonitrile and styrene containing 7.3% by weight of styrene and having an intrinsic viscosity of 1.38 were mixed with 10 parts of sodium thiocyanate and 10 parts ethylene glycol. A stifi gum was formed from which films were pressed which were clear and flexible in the gel state.

Example V An acrylonitrile/vinyl acetate copolymer containing 12% vinyl acetate (intrinsic viscosity of 2.4) was used as in Example IV. The film obtained was bright and clear. The composition from which the film was obtained was a plastic gum.

Example VI An acrylonitrile/methyl acrylate copolymer containing approximately 10% methyl acrylate (intrinsic viscosity of 2.3) was used as in Example IV. The composition formed was a soft gum from which a clear, bright film was pressed at 140 C. and 18,000 lbs. pressure.

Example VII An acrylonitrile/isobutylene copolymer containing 17% isobutylene was treated as in Exam- IV, a gum was obtained which, pressed at 190 C. and 16,000 lbs, formed a brilliantly clear film.

Example X Repetition of the general procedure of Example IV, except that the following polymers were employed, gave substantially the same products: acrylonitrile/hydroxyethyl methacrylate (/10) acrylonitrile/hydroxyethyl methacrylate (85/15) and acrylonitrile/allyloxyethanol (92/8) Example XI Ten parts by weight of polyacrylonitrile (intrinsic viscosity of 1.87) 10 parts of sodium thiocyanate, and 10 parts by weight of n-amyl alcohol were mixed to form a dry dough. A film pressed at 158 C. and 15,000 lbs. was tough, clear, and pliable.

Example XII Isopropyl alcohol was used in place of n-amyl alcohol in Example XI. The film obtained from the composition on pressing was clear and co herent but tended to be brittle. The film was pressed at 158 C. and 15,000 lbs.

Example XIII Glycerin was used in place of ethylene glycol to give a clear, tough, pliable film similar to that of Example 2E. The film was pressed at 180 C. and 15,000 lbs.

Example XIV When the general procedure of Example XI was repeated except that triethanolamine was employed in place of ethylene glycol, a product was obtained which gave clear and coherent films on pressing.

Example XV Ten parts by weight of polyacrylonitrile, 10 parts of potassium thiocyanate, and 10 parts of ethylene glycol were mixed thoroughly. The composition was powdery. A film pressed at C. and 15,000 lbs. was clear and could be drawn after washing in water at 20 C.

Example XVI One hundred parts of polyacrylonitrile (intrinsic viscosity of 1.87), 20 parts by weight of r aifatty alcohol-sulfate surfaceactive agent; and 100. parts of sodium thiocyanate, were mixed thoroughly in a Banbury mixer, following which 80 parts byweight of ethylene glycolwere added slowly with constantlmixing. The rubber-like dough which was obtained was then worked for a few minutes in a Thropp mill andthen run on a three-roll calenderimachine at 38 C. The film which was formedwvastough and clear.

Example X-VII Plastic doughs containin equal, parts by weightof polyacrylonitrile, sodium thiocyanate, and ethylene glycol were formed intomulti-filamerit yarns by using, ascrewextruder and a tenhole spinneret at 180."v C, Clear films were. formed byusing a screw extruder and athree-inch die at 140 C.

The present invention isi eneric to the employment in the compositions. of this invention of acrylonitrile polymers in whichacrylonitrile is the major component. Any such, polymer can be used including copolymers of acrylonitrile with methacrylonitrile, vinylchloride, vinyl acetate, styrene; amino nitrogen containing monomers, e. g., vinylpyridines; quaternary. ammonium monomers, e. g., vinyloxyethyltrimethyl-ammonium chloride. The amount or polymerizable vinylidene monomer. other than the acrylonitrile present in the copolymers is less than 50%. Generally, the amount of acrylonitrile is at least 85%. Acrylon-itrile homopolymer is preferred- The polymer is preferably employed in a finely divided form in the manufacture of the solid coherent compositions of this invention. Mixture with the salt and alcohol is effectedrfaster when the particle, size of the polymer is small, e. g., such as that obtained by the polymerization of acrylonitrile in aqueous systems.

The molecular weight of the polymeris not critical. In general, the polymer should be fiber forming, since utility is usually greatest for such polymers. Polymers having a medium molecular weight, e. g., 5,000 to 100,000, offer a good balance between ease of ,fabrication and physical properties of the resulting shaped and oriented objects.

The amount of. acrylonitrile polymer present in the polymer/sal-t/alcohol mixture is at least 33% and not more than-75%. In general, preferred products have from 40 to 65% polymer.

The present invention-is generic to thiocyahates of lithium, sodium, potassium, magnesium, calcium and zinc, i. e., of elements of atomic numberof 3 to 19 of group -I and of 12,;to ofgroup II. In view of their availability and casein formingthe plastic solid icompositions, thiocyanates of the alkali metals andalkaline earth metals are preferred.

The amount of thiocyanate employed in the production of the; composition of this invention is l8to 46% by weight of the polymer/salt/alcohol. Most useful are amountsof from 25 to The present invention is generic to the employment in the compositions of this invention of an aliphatic alcohol which has at least one oxy, i. e., alcohol, group per five carbons, is liquid at 25.? 0., is soluble to an extent-ofattleast 2% in Water at-20P C., and has a carbon tooxy oxygen ratio of between 1 to l and 5,to1.. Althoughunsaturated alcohols, e. g., allyl and propargyl a1- cohols, can beemployed, the preferred compounds are saturated, i., e., free. from carbon to carbon unsaturation, are hydrocarbon except for alcoholic hydroxyl, and contain not more than six carbons. Thus, there can be employed in-the compositions ofthis inventionmonohydric alcohols, e. g., methyl; ethyl, propyl, butyl, furfuryl, and amyl alcohols; glycols, e. g., ethylene glycol, propylene glycol, and hexamethylene glycol; higher polyhydric' alcohols, e. g., glycerol. and sorbitol; hydroxy ethers, e; g., diethylene, glycol and the monomethyl andmonoethylzethers of ethylene glycoland diethylene glycol. Superior results are obtained with alcohols-that boil above the fabrication temperature. and particularly the glycols of 2-:tov 3 carbons. The. alcohol oxycompound is present'in thecompositions of this. invention in amountsof'from. 5to 33% of the weight of the total ofcpolymer, salt, and alcohol. Water is generally:notabeneficial :since films obtained from compositions containing water are porous. The additionofsurfaceactive agents permits'calendering at lower temperatures to pro.- vide coherent films.

The plastic materials of this invention are generally made bymixing in conventional equip-. ment, e. g., mixingin amortar, milling, Waring Blendor, Thropp mill, or Banbury mixer.

The products of this invention can be modified through the addition of color forming materials, plasticizers, surface active-agents, etc. Examples of such materials are carbonblack, zinc oxide, pigments, zinc stearate, and sodium oleate.

In the fabrication of products from the plastic materials of this invention, a pressure of at least 25 lbs/sq. in. and preferably -1000 lbs/sq. in. at temperatures of atleast 50 C. and preferably -220" C. are employed. With high temperatures, iower pressures can be used.

The plastic materials of this invention are useful for the preparation of molded objects such as films and fibers. They are especially advantageous in that excess water removes the salt rapidly from such molded objects. For example, tests on 6 mil films show that all of the salt and glycol is removed in 15 to 30 seconds by hot water; whereas other agents such as tetramethylene sulfone or dimethylformamide require as high as 240 seconds contact with hot water.

The ingredients of the compositions of this invention are readily available, cheap, and easy to recover for reuse.

A further advantage of the compositions of this invention is that high concentrations of polymer can be used in fabrication of objects such as films and fibers. Solutions containing such high concentrationsof polymer are not susceptible to use in the preparation of such objects. The present invention is of particular advantage in allowing-lowerspinning temperatures and pressures, in reducing the tendency of the acrylonitrile polymer to discolor and decompose, in affording films of superior clarity and in allowing the obtaining of films by calendering.

The foregoing detailed description 1 has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown anddescribedfor obvious modifications will occur to those skilled in the art.

What is claimed is:

l. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer'of major acrylonitrilecontent, l8'- i6% of a metal thiccyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal -tl1iocyanates, and 5-33% of-an aliphatic alcohol which has atleast one alcoholic hydroxyl per'five carbons, is-liquid-at-25 0., and is-soluble in water to the extent of at least 2% at20-' 0., in which composition the weight ratio of salt* to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

2. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer of major acrylonitrile content, 18-46% of a thiocyanate of a metal from those of atomic number of 3 to 19 in group I and of 12 to 30 in group II and 5-33% of an aliphatic alcohol which has at least one alcoholic hydroxyl per five carbons, is liquid at 25 C., and is soluble in water to the extent of at least 2% at 20 C., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

3. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer of major acrylonitrile content, 18-46% of an alkali metal thiocyanate, and 5-33% of an aliphatic alcohol which has at least one alcoholic hydroxyl per five carbons, is liquid at C., and is soluble in water to the extent of at least 2% at 20 C., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

4. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer of major acrylonitrile content, 18-46% of a metal thiocyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal thiocyanates, and 5-33% of a glycol of 2-3 carbons in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to glycol is from 1:1 to 5:1.

5. A solid, essentially non-aqueous composition containing -65% of an acrylonitrile polymer of major acrylonitrile content, 25-40% of a metal thiocyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal thiocyanates, and 5-33% of a glycol of 2-3 carbons in which composition the weight ratio of salt to polymer is from 3:1 to 1:1 and the weight ratio of salt to glycol is from 1:1 to 5:1.

6. A solid, essentially non-aqueous composition containing 40-65% of an acrylonitrile polymer of major acrylonitrile content, 25-40% of a sodium thiocyanate, and 5-33% of a glycol of 2-3 carbons in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to glycol is from 1:1 to 5:1.

7. A solid, essentially non-aqueous composition containing 40-65% of an acrylonitrile polymer of major acrylonitrile content, 25-40% of a metal thiocyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal thiocyanates, and 5-33% of a saturated aliphatic alcohol, hydrocarbon except for alcoholic hydroxyl, of no more than six carbons, of at least one hydroxyl per five carbons, liquid at 25 0., and soluble to the extent of at least 2% in water at 20 C., in which composition the Weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

8. A solid, essentially non-aqueous composition containing 40-65% of an acrylonitrile polymer of major acrylonitrile content, 25-40% of an alkali metal thiocyanate, and 5-33% of a saturated aliphatic alcohol, hydrocarbon except for alcoholic hydroxyl, of no more than six carbons, of at least one hydroxyl per five carbons, liquid at 25 (3., and soluble to the extent of at least 2% in water at 20 C., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

9. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile homopolymer, 18-46% of a metal thiocyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal thiocyanates, and 5-33% of an aliphatic alcohol which has at least one alcoholic hydroxyl per five carbons, is liquid at 25 C., and is soluble in water to the extent of at least 2% at 20 C., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

10. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile homopolymer, 18-46% of an alkali metal thiocyanate, and 5-33% of an aliphatic alcohol which has at least one alcoholic hydroxyl per five carbons, is liquid at 25 C., and is soluble in water to the extent of at least 2% at 20 0., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

11. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile homopolymer, 18-46% ofan alkali metal thiocyanate, and 5-33% of a saturated aliphatic alcohol, hydrocarbon except for alcoholic hydroxyl, of no more than six carbons, of at least one hydroxyl per five carbons, liquid at 25 C. and soluble to the extent or at least 2% in water at 20 C., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

12. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile homopolymer, 18-46% of an alkali metal thiocyanate, and 5-33% of a glycol of 2-3 carbons, in which composition the ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to glycol is from 1:1 to 5:1.

13. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer of major acrylonitrile content, any comonomer being monoethylenically unsaturated and present in the polymer in minor amount, 18-46% of a metal thiocyanate of the class consisting of alkali metal thiocyanates and alkaline earth metal thiocyanates, and 5-33% of a saturated aliphatic alcohol, hydrocarbon except for alcoholic hydroxyl, of no more than six carbons, of at least one hydroxyl per five carbons, liquid at 25 C., and soluble to the extent of at least 2% in water 'at 20 0., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

14. A solid, essentially non-aqueous composition containing 33-75% of an acrylonitrile polymer of major acrylonitrile content, any comonomer being monethylenically unsaturated and present in the polymer in minor amount, 18-46% of an alkali metal thiocyanate, and 5-33% of a saturated aliphatic alcohol, hydrocarbon except for alcoholic hydroxyl, of no more than six carbons, of at least one hydroxyl per five carbons, liquid at 25 C., and soluble to the extent or at least 2% in water at 20 0., in which composition the weight ratio of salt to polymer is from 3:10 to 1:1 and the weight ratio of salt to alcohol is from 1:1 to 5:1.

Cresswell Dec. 12, 1950 Cresswell July 3, 1951 Number 

1. A SOLID, ESSENTIALLY NON-AQUEOUS COMPOSITION CONTAINING 33-75% OF AN ACRYLONITRILE POLYMER OF MAJOR ACRYLONITRILE CONTENT, 18-46% OF A METAL THIOCYANATE OF THE CLASS CONSISTING OF ALKALI METAL THIOCYANATES AND ALKALINE EARTH METAL THIOCYANATES, AND 5-33% OF AN ALIPHATIC ALCOHOL WHICH HAS AT LEAST ONE ALCOHOL HYDROXYL PER FIVE CARBONS, IS LIQUID AT 25* C., AND IS SOLUBLE IN WATER TO THE EXTENT OF AT LEAST 2% AT 20* C., IN WHICH COMPOSITION THE WEIGHT RATIO OF SALT TO POLYMER IS FROM 3:10 TO 1:1 AND THE WEIGHT RATIO OF SALT TO ALCOHOL IS FROM 1:1 TO 5:1. 